Water-soluble azo dyestuffs



United States Patent Ofifice 3 ,297,678 Patented Jan. 10, 1967 3,257,678 WATERSOLUBLE AZO DYESTUFFS Rudolf Kiihne, Fritz Meininger, andLothar Hiirnig,

Frankfurt am Main, Germany, assignors to Farbwerke HoecllstAlrtiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main,Germany, a corporation of Germany No Drawing. Filed Oct. 25, 1963, Ser.No. 318,794 Claims priority, application Germany, Oct. 26, 1962,

6 Claims. (Cl. 260--163) The present invention relates to newwater-soluble azo dyestuffs and a process for preparing them; moreparticularly the present invention relates to water-soluble azodyestuffs of the following formulae wherein F represents the radical ofa monoor disazo dyestuif molecule which may be substituted by groupsimparting solubility in water, R represents a hydrogen atom or an alkylgroup having 1 to carbon atoms, Z represents an organic or inorganicacid radical, X represents a straight-chain or branched-chain alkylenegroup having 1 to 4 carbon atoms, Y represents a halogen atom or anoxygen, nitrogenor sulfur-containing radical and n stands for theinteger 1 to 2.

We have found that new valuable water-soluble azo dyestuffs can 'beobtained by (a) coupling aromatic diazo-, diazoazoor tetrazo compoundswith coupling components, both components may contain groups impartingsolubility in water, for example sulfonic acid or carboxylic acidgroups, and at least one of the two components contains one or moregroups of the following formulae respectively, which may be linkeddirectly or through a bivalent organic bridging member, for example analkylene group, to an aromatic nucleus of the dyestuff molecule andwherein R represents a hydrogen atom or an alkyl group having 1 to 5carbon atoms, Z represents an organic or inorganic acid radical, Xrepresents a straight-chain or branched-chain alkylene group having 1 to4 carbon atoms and y represents a halogen atom or an oxygen-, nitrogenorsulfur-containing radical, or by (*b) reacting watersoluble azodyestuffs which contain at least one secondary amino group of thefollowing formula with an acylating agent introducing the group such assulfonic or carboxylic acid groups, which may possibly be present in theazo dyestulf molecule in addition to the characteristic groups 1) or(2), depends on the molecular weight of the dyestuff. If the molecularweight of the azo dyestuff is relatively low and if the group of theabove Formulae 1 and 2 respectively, present in the molecule contains agroup imparting solubility in water, it is not necessary that anadditional group imparting solubility in water, for example a sulfonicor carboxylic acid group, be present. If, however, the dyestuif moleculecontains only a group of Formula 2 in which Y is no group impartingsolubility in water or a group of Formula 1 in which Z and Y are nogroups imparting solubility in water, or if the dyestuff has arelatively high molecular weight, it is advantageous that the monoazodyestuff contain, per azo group, at least two, and the disazo dyestuffat least three, of such additional groups imparting solubility in waterto ensure an appropriate solubility in water.

As organic or inorganic acid radicals Z there may be mentioned, forexample, the radicals OSO H and -OOCCH and the halogens. As examples ofoxygen-, nitrogenor sulfur-containing radicals Y there may be named thegroups OH, -CN, OSO H, SO H, -COOH, COO-alkyl,

-SO =alkyl, -CONH ,-O=alkyl andN(alkyl) Exemplary of suitable acylatingagents introducing the group SO CH=CHR or SO2CH2CHZ into the azodyestuif molecule are carbyl sulfate, vinyl sulfonic acid chloride andB-chlorethane-sulfonic acid chloride.

The preparation of the new azo dyestuffs according to method (a) fromdiazo, diazoazo or tetrazo compounds and coupling components is carriedout under the conditions usually applied for diazotization and couplingprocesses.

The reaction of water-soluble azo dyestuffs containing at least onegroup corresponding to Formula 3 with acylating agents according tomethod (b) may be carried out according to the processes known for theacylation of amino groups, for example, by a reaction of the said azodyestuffs with vinyl sulfonic acid chloride or B-chlorethanesulfonicacid chloride, dissolve-d in an organic solvent which is inert under thereaction conditions, for example dimethyl formamide, acetone, methylenechloride, benzene or toluene, in the presence of an acid-binding agent,for example sodium hydrogen carbonate, sodium acetate, an inert tertiaryamine, for example dimethylamine triethylamine or pyridine, or by anaddition reaction of carbyl sulfate with the secondary amino group (3)of the azo dyestuffs in water or in an inert organic solvent, forexample nitrobenzene or ethylene chloride, at temperatures within therange of about 40 to C., if desired in the presence of tertiary amines,for example triethylamine.

The compounds used as starting components according to method (a) may beprepared in the same manner by reacting the corresponding aromaticamines (diazo components) and coupling components, respectively,containing group (3) with the acylating agents in the above manner bycondensation with splitting oif of hydrogen halide or by an additionreaction.

3 4 Exemplary of diazo components to be used in the 1,3-dihydrxybenzene,process of the invention and containing at least one of the2,4-dihydroxybenzophenone, above mentioned characteristic groups ofFormula 1 or hydroxynaphthalene, 2 are the following compounds and theiralkali metal salts, 2-hydroxy-7benzoylamino-naphthalene, respectively:2-hydroxynaphthalene-3carboxylic acid-methyl ester,

2-hydroxynaphthalene-6-sulfonic acid amide, dihydroxy-naphthalene,

arylamides of 2-3-hydroxynaphthoic acid,1-phenyl-5-pyrazolone-3carboxylic acid-amide,

3- (N-p-cyanoethyl-N-ethionylamino)1-aminobenzene,4-(N-B-cyanoethyl-N-ethionlamino)1-aminobenzene, 3-N-B-cyanoethyl-N-ethionylamino) 4-methoxy- 1- aminobenzene, 5-(N-fl-chloroethyl-N-ethionylamino 2-methyl- 1- P3 12010116,

aminobenz n Z-hydroxyqumo me,

Z-hydroxycarbazole, 3-hydroxycarbazole,

2-hydroxydiphenylene oxide 3-N-fi-chloroethyl-N-fichloroethylsulfonylaminol-aminobenzene, 3-N-ficyanoethyl-Nvinylsulfonylamino 1- aminobenzene, and the sulfonicacid or carboxylic acid group-containing3-(N-B-carboxyethyl-N-ethionylamino)-1-aminoderivatives of the abovecompounds.

benzene, Exemplary of coupling components contaming a group3-(N-p-carbethoxy-ethyl-Nethionylamino)-1-aminoor l4(N'fl'cyanoethyl'N'ethlonylamlrlo)'1 benzene, acetoacetylamruobenzene,6-(N-B-cyanoethyl-N-ethionyl- 4 (N carbethOXy methy1 N ethionylamino) 1amino amino)-l-hydroxynaphthalene-3-sulfon1c acid and cornbenzene poundsof the following formula (HOaSh NH( J (|fNH- /XY N N N\ (!3 SO2CHz-CHZ5-(N-fi-cyanoethyl-N-ethionylamino)2-chloro-1- wherein R, X, Y and Zhave the meanings given above aminobenzene, and n stands for the integer1 or 2. 4-(N-fl-cyanoethyl-N-ethionylamino)-6-amino-l,3- The dyestuffsmay also be prepared in a manner such dimethylbenzene, that suitablegroups are preformed in the dyestuff prod-4-(N{3-cyanoethyl-N-ethionylamino)2-arnino-1-3- ucts and the groups ofFormula 1 and 2 are finally formed dimethylbenzene, only after thepreparation of the dyestuffs. For example,3-(N5hydroxyethyl-N-ethionylamino)1-arninoby coupling diazotized3-(N-Bchloroethyl-N-isethionylbenzene, amino)-1-aminobenzene, withhydroxynaphthalene 43-(N-fi-hydroxyethyl-Nisethionylamino)1-aminosulfonic acid, a monoazodyestulf can be obtained which benzene-disulfuric acid ester, does notyet contain the radical Z of the group of For-4-(N-fl-chloroethyl-N-p-chloroethylsulfonylamino)- ula 1. This radicalcan subsequently be introduced by l-aminobenzene esterification of thealiphatic hydroxyl group, for example h f 11 or 1 by treatment withSlJlfllI'lC acid. and compounds of t e 0 Owing f mu a6 Dyestuffs orinitial dyestutf products containing group (2) in the molecule may alsobe obtained by treating suitg B N able starting compounds containing agroup of Formula HN l with an acid-binding agent such as sodiumcarbonate or sodium hydroxide, the acid radical Z being split off (5)with the formation of a vinyl sulfonyl amino group suband stituted atthe nitrogen atom.

The dyestuffs of the invention are suitable for use in the dyeing orprinting of a wide variety of material, for

example wool, silk, leather and linear polyamides. They s02 CH=CH R (6)are particularly suitable for producing dyeings and printrespectively,wherein R, X, Y and Z have the meanings ings that are fast to washing orcellulose containing magiven above and B is a direct linkage or a --CHterials of fibrous structure, for example, regenerated cel- -O, S, CO,NH, -SO CO lulose and particularly cotton. The dyestuffs are applied NH,-SO NH or N:N bridging member.

If coupling components containing at least one group of to the cellulosefiber by treating the material with an aqueous solution of the dyestuifin the presence of an Formula 1 or 2 are used, any desired primaryaromatic acid binding agent such as sodium hydroxide, sodiumbidiazotizable amines may be used as diazo components. carbonate ortrisodium phosphate, or by treating it with As coupling components theremay be used all coma printing paste in the presence of an acid-bindingagent.

pounds of the benzene or naphthalene series that are In addition toacid-binding agents or substances capable capable of coupling owing tothe presence of an amino of giving off acid-binding agents, the dyestufisolutions group or an aromatically bound hydroxyl group. There orprinting pastes may contain urea, urethanes or watermay further be usedpyrazolone, quinoline or Z-hydroxysoluble amides of aliphatic carboxylicacids, for example diphenylenc OXidc the derivatives thereof, of keto'forrnamide, acetamide or malonic acid diamide. The methylene Compoundsthat contain a methylene group treatment with the acid-binding agent maybe carried out that i$ capable of Coupling in neighboring POsition to anbefore, during or after the application of the dyestuff, enolllable ketoP- Exemplary of Such compounds if desired at elevated temperatures. Thedyestuffs of the are invention may also be used for printing mixedcellulose- 4-methyl-1hydroxybenzene, polyester fabric. For this purpose,the textile material is 4-acetylamino-l-hydroxybenzene, printed with aprinting paste containing an acid-binding The dyestuffs of the inventionyield pure tints which are distinguished by good fastness properties tolight and particularly by a very good fastness to washing.

As compared with the next comparable dyestuffs known, for example, fromGerman Patent 1,107,356 and containing the group of the followingformula SO2CH=CH2 in the dyestuif molecule, the dyestuffs of theinvention have the advantage that they enable considerably fullerdyeings and prints that can more easily be fixed to be obtained oncellulose fibers.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto, the parts being by weight unlessotherwise stated and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter.

Example 1 37.1 parts of the potassium salt of 3-(N-B-cyanoethyl-N-ethionylamino)-1-aminobenzene of the formula NHz were dissolved in amixture of 190 parts by volume of water and 50 parts of aqueoushydrochloric acid (d. 1.15 By slowly adding a 5 N solution of sodiumnitrite, the said amine was diazotized at a temperature within the rangeof to C. When the diazotization was terminated a neutralized solution of22.4 parts of l-hydroxynaphthalene-4-sulfonic acid in 200 parts byvolume of water was added to the solution of the diazo compound and thepH value was adjusted to 4.5 by adding sodium bicarbonate. When thecoupling was complete, the dye stuff so obtained was salted out withpotassium chloride, filtered off washed with dilute potassium chloridesolution and finally dried in vacuo at a temperature within the range of40 to 50 C.

A powder was obtained which dissolved in water with the appearance of anorange color. It dyed wool bright orange-red tints. By printing oncotton with a printing paste made of the dyestutf and containing also analkali, for example sodium bicarbonate or trisodium phosphate andsteaming at a temperature within the range of 100 to 105 C.,orange-colored prints were obtained which were distinguished by verygood fastness properties, particularly by a very good fastness to wetprocessing.

By using, instead of 22.4 parts of l-hydroxynaphthalene- 4-sulfonicacid, an equivalent amount of1-(4'-sulfophenyl)-3-methyl-pyrazolone-(5), while otherwise proceedingas described above, a water-soluble yellow dyest-uff was obtained whichdyed cotton full yellow tints which were fast to boiling soda.

The 3 (N-fl-cyanoethyl-ethionylamino) l-aminobenzene used as the diazocomponent may be prepared in the following manner:

1-amino-3-nitrobenzene is condensed at 120 C. with acrylonitrile in thepresence of glacial acetic acid and copper acetate to yield3-(N-p-cyanoethylamino)-1-nitrobenzene melting at 97 C. and thiscompound is reacted with carbyl sulfate in nitrobenzene to yield3-(N-B-cyanoethyl-N-ethionylamino)-1-nitrobenzene. (By subjecting thelast-mentioned compound at room temperature to the action of dilutesodium hydroxide solution,3-(N-fl-cyanoethyl-N-vinylsulfonylamino)-1-nitrobenzene melting at C. isobtained; by subjecting it to the action of dilute hydrochloric acid,3-(N-,8-cyanoethyl-N-fi-hydroxyethylsulfonylamino)-l-nitrobenzenemelting at 96 C.). By reducing the3-(N-Bcyanoethyl-N-ethionylamino)-1-nitrobenzene with iron,3-(N-,8-cyanoethyl-N-ethionylamino)- l-aminobenzene is obtained.

Example 2 38.5 parts of the potassium salt of S-(N-fl-cyanoethyl-N-ethionyl amino)-2-metl1yl-1-ami nobenzene of the formula weredissolved in a mixture of 250 parts by volume of water and 60 parts ofaqueous hydrochloric acid (d. 1.15) and diazotized with sodium nitrite.When the diazotization was terminated, the solution of the diazocompound was run into a solution of 30.4 parts of 1-naphthol-3,6-disulfonic acid in 210 parts by volume of water which had beenneutralized with sodium hydroxide solution. Then the pH value wasadjusted to 5.0 by the addition of sodium bicarbonate. When the couplingwas complete, the dyestutf was salted out with potassium chloride,filtered off and dried at 60 C. in vacuo.

With the dyestufi' so obtained a scarlet print of good fastnessproperties was obtained on cotton using the printing-steaming method.

When, instead of 30.4 parts of 1-naphthol3,6-disulfonic acid, 25.4 partsof 1-(4-sulfophenyl)-3-methylpyrazolone- (5) were used, while otherwiseproceeding as described above, a yellow dyestufi was obtained which dyedcotton reddish yellow tints of very good fastness to washing.

The 5-(N-B-cyanoethyl-N-ethionylamino)-2-methyl-laminobenzene used asthe diazo component may be prepared as follows:5-nitro-2-methyl-1-aminobenzene melting a 79 C. is condensed at 120 C.with acrylonitrile in the presence of glacial acetic acid and copperacetate to obtain 4-(N-fi-cyanoethylamino)-2methyl-1-nitrobenzenemelting at a temperature within the range of 83 to 85 C. By reacting thecyano compound so obtained with carbyl sulfate in nitrobenzene,S-(N-cyanoethyl N ethionylamino) 2 methyl 1 nitrobenzene is obtainedwhich is converted intoS-(N-B-cyanoethyl-N-ethionylamino)-2-methyl-1-aminobenzene by reductionwith iron powder.

Example 3 37.1 parts of the potassium salt of 3-(N-B-cyanoethyl-N-ethionylamino)-1-aminobenzene of the formula CHz-CHz-CN werediazotized in the manner described in Example 1. The diazo solution soobtained was run at a temperature within the range of 0 to 5 C. into asolution of 28.9 parts of 1-(2'-chloro-5-sulfop-henyl)-3methyl-pyrazoline-(S), 12 parts of sodium carbonate and 5 parts ofsodium hydroxide in parts by volume of water. Then 35 parts ofcrystallized sodium acetate were added.

When the coupling was complete the dyestufif so obtained was salted outby the addition of potassium chloride, filtered off and dried at 50 C.in vacuo.

The yellow dyestuff powder which dissolved in water with a yellow colordyed silk yellow tints of good fastness properties.

Under the action of heat in the presence of sodium bicarbonate, thedyestutf yielded a yellow print on cotton which was fast to boilingsoda.

The following table indicates the diazo and coupling components offurther azo dyestuffs obtainable in a manner analogous to that describedin Example 3 and the tints obtained with these dyestuffs on cotton.

were dissolved in a mixture of 200 parts by volume of water, 50 .partsby volume of acetone and 60 parts by volume of 5 N-hydrochloric acid andiazotized at a temperature within the range of to C. When thediazotization was terminated, the solution was adjusted to a pH value of6 to 6.5 with sodium bicarbonate. Then a solution of 33.8 parts of1-(2-methyl 6 chloro 4 sulfophenyl) 3 methyl pyrazolone (5) and 16 partsof sodium hydroxide solution of 33 weight-percent strength in 110 partsby volume of water was run in at C. After stirring for 1 hour, 28 partsof crystallized sodium acetate were added. When the coupling wascomplete, the dyestufl? was isolated and dried.

A powder was obtained which dissolved in water with yellow color andwhich could be printed on cotton in the following manner: 20 parts ofthe dyestuif were dissolved with 50 parts of urea in 200 parts of hotwater. The solution so obtained was mixed, while stirring, with 400parts of a thickening consisting of 40 parts of sodium alginate and 960parts of water and 20 parts of sodium bicarbonate. The paste was thenmade up to 1000 parts with water and thickening.

Cotton fabric was printed with the paste so obtained, dried, subjectedfor 5 minutes to steaming at a temperature of 101 to 103 C., rinsed withcold and then with hot water, soaped at the boil, rinsed again anddried. A yellow print of excellent fastness properties was obtained.

The 3 (N 5 eyanoethyl N vinylsulfonylamino) l-aminobenzene used as thediazo component may be prepared as follows: 1-amino-3-nitrobenzene iscondensed at 120 C. with 'acrylonitrile in the presence of glacialacetic acid and copper acetate to obtain 3-(N 9 cyanoethylamino) 1nitrobenzene and the latter is reacted with carbyl sulfate innitrobenzene to obtain 3 (N B cyan-oethyl N ethionylamino) 1nitrobenzene. By reduction with iron this compound is converted into 3-(N [3 cyanoethyl N ethionylamino) 1 aminobenzene which is treated atroom temperature with dilute sodium hydroxide solution to obtain theabove mentioned diazo component melting at 75 to 77 C.

The following table indicates the diazo and coupling components offurther azo dyestuffs obtainable in the manner described in Example 4and the tints obtained therewith on cotton.

A solution of 20.8 parts of the potassium salt of 3-(N- carbmethoxymethyl N ethionylamino) 1 aminobenzene of the following formula in 300parts by volume of water was mixed with 80 parts by volume of 2N-hydrochlon'c acid and diazotized at 5 C. When the diazotization wasterminated, the diazonium salt solution was neutralized with sodiumbicarbonate and combined with a solution of 15.2 parts of the sodiumsalt of 6 -aoetylamino 1 hydroxynaphthalene 3 sulfonic acid and 10 partsof crystallized sodium acetate in parts by volume of water. When thecoupling was complete, the dyestuff was isolated and dried at 40 C.

With the dyestuff so obtained cotton was printed according to theprinting-steaming method, a bright orange print of very good fastness towashing being obtained.

The 3-(N carbmethoxy methyl-N-ethionylamino)- l-aminobenzene used as thediazo component may be prepared in the following manner: 3 -(Ncarbmethoxy methylamino) 1 nitrobenzene melting at a temperature of 99to 101 C. is reacted in nitrobenzene with carbylsulfate to obtain 3 (Ncarbmethoxy methyl N ethionylarnino) 1 nitrobenzene. (By treating thecompound at room temperature with dilute sodium hydroxide solution, 3 (Ncarbmethoxy methyl N vinylsulfonylamino) 1 nitrobenzene melting at 104.5C. and 3 (N carboxy methyl N vinylsulfonylamino) l-nitrobenzene meltingat 119 C. are obtained.) By catalytic reduction of the 3 (N carbmethoxymethyl)- N ethionylamino 1 nitrobenzene in the presence of Raney nickel,3 carbmethoxy methyl N ethionylamino)-1-arninobenzene is obtained.

Example 6 21.0 parts of the potassium salt of 3 (N B carbmethoxy-ethyl Nethionylamino) 1 aminobenzene of the following formula were dissolved in220 parts by volume of water and then 20 parts by volume of concentratedaqueous hydrochloric acid were added. By the addition of a 5 N-solutionof sodium nitrite at to C. the said amine was diazotized. When thediazotization was terminated, a neutralized solution of 12 parts 1hydroxynaphthalene 4 sulfonic acid in 150 parts by volume of water wasrun into the diazo solution and the pH value was adjusted to 4.5 by theaddition of sodium bicarbonate. When the coupling was complete, theorange-red dyestuff was isolated and dried. The dyestuff had propertiessimilar to those described in Example 1.

The 3-(N-B-carbmethoxy-ethyl-N-ethionylamino) 1- aminobenzene used asthe diazo component may be prepared as follows:

1-amino-3-nitrobenzene is condensed at 100 C. with acrylic acid methylester in the presence of catalytic amounts of glacial acetic acid andcopper acetate to obtain 3-(N-fi-carbmethoxy-ethylamino) 1 nitrobenzenemelting at 86 to 87 C. (This compound may also be obtained bycondensation of acrylic acid with 1-amino-3- nitrobenzene in thepresence of copper acrylate at a temperature within the range of 100 to120 C. or by saponification of 3-(N-[3-cyanoethylamino)-1nitrobenzenewith sulfuric acid of 75% strength and subsequent esterification of theresulting 3-(N-B-carboxyethylamino)- l-nitrobenzene melting at 122 C.with methanol in the presence of sulfuric acid.) The es-ter so obtainedis reacted with carbyl sulfate in nitrobenzene to obtain 3-(N-fi-carbmethoxyethyl-N-ethionylamino) 1 nitrobenzene (melting point ofthe potassium salt 120 C. with decomposition). (By subjecting thiscompound at room temperature to the action of dilute sodium hydroxidesolution, 3 (N [3 carbmethoxyethyl-N-vinylsulfonylamino)-1-nitrobenzenemelting at 45 C. is obtained; by subjecting it in the hot to the actionof dilute hydrochloric acid, 3 (N [3carboxyethyl-N-fi-hydroxyethylsulfonylamino)-1-nitrobenzene melting at106 C. is obtained.) By catalytic reduction of the3-(N-B-carbmethoxy-ethyl- N-ethionylamino)-l-nitrobenzene in thepresence of Raney nickel, 3-(N-fi-carbmethoxy-ethyl-N-ethionylamino) 1-aminobenzene is obtained.

The following table indicates the diazo and coupling components offurther azo dyestuffs obtainable in the manner described in Example 6and the tints obtained therewith on cotton.

were diazotized in usual manner. The aqueous solution of the diazocompound so obtained was stirred at a temperature within the range of 0to 10 C. into a solution of 23.5 parts of1-hydroxynaphthalene-S-sulfonic acid and 4 parts of sodium hydroxide in150 parts by volume of water. After the reaction mixture had beenadjusted to a pH of 6.8 with sodium bicarbonate, it was saponified 10with 15 parts of crystallized sodium acetate and stirred until couplingwas complete. The dyestutf so obtained was salted out with sodiumchloride, filtered OE and dried in vacuo at a temperature within therange of 50 to 60 C. The dyestuff dyed cotton and wool red tints of goodfastness properties.

Example 8 A solution of 19.8 parts of the potassium salt of 4-(N-/3ch10roethyl-N-ethionylamino)-1-aminobenzene of the following formula in150 parts by volume of water and 30 parts by volume of 5 N-hydrochloricacid was diazotized at a temperature between 0 and 5 C. When thediazotization was terminated, the pH value of the solution was adjustedto 6 to 6.5 with sodium bicarbonate. Then a solution of 15.5 parts of1-(2-methyl-6-chloro-4'-sulfophenyl)-3-methylpyrazolone-(S) and 7 partsof sodium hydroxide solution of 33 weight-percent strength in 70 partsby volume of water was run into the diazo solution and the reactionmixture was buffered by adding 17 parts of crystallized sodium acetate.When the coupling was complete, the dyestuff was isolated and dried at50 C.

The brown-yellow dyestufi powder dissolved in water with a yellow color.It dyed wool and cotton yellow tints of good fastness properties.

When, instead of 19.8 parts of the potassium salt of4-(N-B-chloroethyl-N'ethionylamino) 1 aminobenzene, 20.5 parts of thecompound of the following formula lTIHz SOFGI'I2 CH O sO3I and, inanother instance, 14.9 parts of the compound of the following formulawere used as the diazo component, while otherwise proceeding asdescribed above, yellow dyestuffs of similar properties were obtained.

The 4- N-fi-chloroethyl-N-ethionylamino 1 -aminobenzene used as thediazo component may be prepared as follows: 1-chloro-4-nitrobenzene isreacted at to C. with ethanolamine in pyridine to obtain 4-(N-B-hydroxyethylamino)-1-nitrobenzene melting at 110 C. and the latter issubsequently converted with thionyl chloride in benzene into4-(N-B-chloroethylamino)-1-nitrobenzene melting at 87 C. The lastmentioned compound is then reacted with carbyl sulfate in nitrobenzeneto obtain 4- N-B-chloroethylN-ethionylamino 1 -nitrobenzene. Bycatalytic reduction in the presence of Raney nickel, the compound isconverted into 4-(N-[3-chloroethyl-N-ethionylamino -1-aminobenzene.

1 1 Example 9 21.7 parts of the potassium salt of3-(N-,8-carbmethoxyisopropyl-N-ethionylamino)-l-aminobenzene of thefollowing formula were diazotized in usual manner. To the diazo solutionso obtained, 12.5 parts 7-amino-1-hydroxy-naphthalene-3- sulfonic acidand subsequently 33 parts of crystallized sodium acetate were added. Thedyestuff so obtained was salted out with sodium chloride and isolated.

The dyestuff constituted a red powder which was readily soluble in waterand dyed cotton and wool fast red tints.

The 3 (N-B-carbmethoxyisopropyl-N-ethionylamino)- l-aminobenzene used asthe diazo component may be prepared as follows: 1-amino-3-nitrobenzeneis condensed at 110 C., with crotonic acid in the presence of catalyticamounts of glacial acetic acid to obtainB-(N-fl-carboxyisopropylamino)-1-nitrobenzene melting at 124 C. and thecarboxylic acid so obtained is esterified with methanol in the presenceof sulfuric acid. The ester which has a melting point of 55 to 56 C. isreacted in nitrobenzene with carbyl sulfate to yield3-(N-fl-carbmethoxyisopropyl- N-ethionylamino)-l-nitrobenzene having amelting point of 175 to 178 C. (decomposition). By catalytichydrogenation in the presence of Raney nickel3-(N-B-carbmethoxyisopropyl N-ethionylamino)-1-aminobenzene is obtained.

Example 10 20.8 parts of the potassium salt of4-(N-carbmethoxymethyl-N-ethionylamino)-1-aminobenzene of the followingformula l CHr'C-OCH;

SOr-CHz-CHr-O-SChK were diazotized in the manner described in Example 5.When the diazotization was terminated the diazonium salt solution wasneutralized with sodium bicarbonate and combined with a solution of 13.0parts of the sodium salt of 1-hydroxynaphthalene-4-sulfonic acid and 10parts of crystallized sodium acetate in 100 parts by volume of water.When the coupling was complete, the red dyestuff so obtained wasisolated and dried.

Dyeings could be prepared with the dyestulf by proceeding as follows:83.5 parts of a viscose rayon fabric were treated, while being wellmoved, for 1 hour at 20 C. with 1000 parts by volume of a liquorcontaining 5 parts of the dyestuff, 50 parts of sodium sulfate and partsof sodium hydroxide. The fabric was then rinsed at the boil and dried. Abright scarlet dyeing of very good fastness to washing was obtained.

The 4 (N carbmethoxymethyl-N-ethionylamino)-1- aminobenzene used as thediazo component may be prepared as follows:4-(N-carbmethoxymethylamino)-l-nitrobenzene melting at 177 C. is reactedwith carbyl sulfate in nitrobenzene to obtain 4-(N-carbmethoxymethyl-N-ethionylamino)-l-nitrobenzene which is converted into 4 (Ncarbmethoxymethyl-N-ethionylamino)-1-aminobenzene by catalytichydrogenation in the presence of Raney nickel.

12 Example 11 20.7 parts of the potassium salt of 4-(N-B-cyanoethyl- Nethionylamino) 6-amino-1,3-dimethylbenzene of the 5 following formulawere diazotized in usual manner, coupled withl-hydroxynaphthalene-4-sulfonic acid as described in Example 10 andisolated. The dyestulf so obtained constituted a red powder.

The dyestuff could be thermofixed on cellulose fabric by proceeding asfollows: parts of the dyestuff were dissolved with 50 parts of urea in200 parts of hot water. To the solution so obtained 400 parts of anaqueous alginate thickening of 8 weight-percent strength which wasresistant to alkalies and 20 parts of sodium bicarbonate were added,while stirring. The mixture was made up to 1000 parts with water andthickening. With the paste so obtained prints were produced on cellulosefabric. The dyestufi was fixed by subjecting the printed fabric for 3minutes to a dry heat-treatment at 140 C. By soaping 3 at the boil andrinsing a bright scarlet print of very good fastness to washing wasobtained.

The compound used as the diazo component may be prepared as follows:6-nitro-4-amino-1,3-dimethylbenzene melting at a temperature of 123 to124 C. is reacted with acrylonitrile to obtain4-(N-fi-cyanoethylamino)-6- nitro-1,3-xylene melting at 107.5 C. and thelatter is reacted with carbyl sulfate to obtain 4-(N-fl-cyanoethyl- Nethionylamino)-6-nitro-1,B-dimethylbenzene. By reducing this compound inthe presence of iron, 4-(N-B- cyanoethyl N ethionylamino)6-amino-1,3-dimethylbenzene is obtained.

When, instead of 20.7 parts of the potassium salt of 4 (Nfi-cyanoethyl-N-ethionylamino)-6-an1ino-1,3-dimethylbenzene, the sameamount of the potassium salt of 4 (N 13cyanoethyl-N-ethionylamino)-2-amino-1,3-dimethylbenzene was used, whileotherwise proceeding as described above, a yellowish red dyestulf ofsimilar good properties was obtained.

The 4-(N-fl-cyanoethyl-N-ethionylamino)-2-amino-1,3-

dimethylbenzene used as the diazo component may be prepared in thefollowing manner: 2-nitro-4-amino-1,3- dimethylbenzene melting at 78 C.is reacted with acrylonitrile to obtain4-(N-B-cyanoethylan1ino)-2-nitro-1,3- dimethylbenzene melting at 114 C.which is converted 6 into 4 (Nfi-cyanoethyl-N-ethionylamino)-2-nitro-1,3- dimethylbenzene by reactingwith carbyl sulfate. By reduction in the presence of iron powder, 4-(N-8-cyanoethyl N ethionylamino)-2-amino-1,3-dimethylbenzene is obtained.(4 (N ,B-cyanoethyl-N-ethionylamino)-6- 6 amino-1,3-dimethylbenzene canbe prepared in analogous manner.)

Example 12 18 parts of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acidwere dissolved in 200 parts by volume of water and 4 parts by volume ofsodium hydroxide solution of 33 weight-percent strength and combinedwith a mixture of parts of ice, 30 parts by volume of 2 N-hydrochloricacid and 200 parts by volume of water. The solution so obtained wasmixed with a diazonium salt solution obtained by diazotizing 19.6 partsof 4-chloro-3-(N-fl-cyano- 13 ethyl-N-ethionylamino)-1-arninobenzene ofthe following formula CHr-CHr-CN N 01 SOrCHz-OHrO-SOsK The reactionmixture was maintained at a pH of about 2 by the addition of sodiumacetate.

5.3 parts of aminobenzene were diazotized in known manner in a mixtureof 60 parts by volume of water and 14 parts of aqueous hydrochloricacid. When the diazotization was terminated, the solution of thediazonium compound was combined with the solution of the monoazodyestuif prepared as described above and having the following formulaHzN OH By the addition of sodium carbonate the pH value was adjusted to6 to 6.5. When the coupling was complete the disazo dyestuff obtainedwas isolated by salting out with potassium chloride and subsequentfiltration.

The disazo dyestuif so obtained dyed wool blue-black to black tints.

The 4-chlo1'o-3-(N-fi-cyanoethyLN-ethionylamino)-1- aminobenzene used asthe diazo component may be prepared as follows:4-chloro-3-amino-1-nitrobenzene is reacted with acrylonitrile to obtain4-chloro-3-(N-fi-cyanoethylamino)-1-nitrobenzene which is reacted withcarbyl sulfate to obtain 4-chloro-3-(N-fi-cyanoethyl-N-ethionylamino)-1-nitrobenzene. The latter is reduced in the presence ofiron to obtain 4-chloro-3-(N-B- cyanoethyl-N-ethionylamino-1-aminobenzene.

The following table indicates the diazo and coupling components offurther disazo dyestufis which can be obtained in a manner analogous tothat described in this example and the tints obtained therewith oncotton.

CHr-CH2CN N 10.1 parts of the potassium salt of 4-(N-[3-cyanoethyl-N-ethionylamino -1-(4-aminobenzoylamino) -benzene of the followingformula were dissolved in a mixture of 300 parts by volume of water, 50parts of ice and 60 parts by volume of 2 N- hydrochloric acid anddiazotized with sodium nitrite. To the diazo solution so obtained 9parts of 8-acetylamino-1- hydroxynaphthalene-3,6-disulfonic acid wereadded.

Subsequently sodium carbonate was introduced until a pH of 5.5 wasobtained. The dyestuif was salted out with sodium chloride, filtered oifand dried in vacuo at 50 C. A red powder was obtained which dissolvedreadily in water with a red color. In the presence of acid bindingagents such as sodium bicarbonate and sodium carbonate the dyestuif dyedcotton from baths containing salt red tints of very good wet fastnessproperties.

The 4-(N-fl-cyanoethyl-N-ethionylamino) -1-(4'-aminobenzo1amino)-benzeneused as the diazo component may be prepared as follows:l-amino-4-nitrobenzene is condensed at a temperature within the range ofto 140 C. with acrylonitrile in the presence of glacial acetic acid andcopper acetate to obtain 4-(N-,B- cyanoethylamino)-1-nitrobenzenemelting at a temperature of 128 to 130 C. and this compound is convertedwith carbyl sulfate in nitrobenzene into 4-(N-fl-cyanoethyl-N-ethionylamino)-1-nitrobenzene. By reducing the latter with iron,4-(N-6-cyanoethyl-N-ethionylamino)-1- aminobenzene is obtained which isreacted with 4-nitrobenzoylchloride to obtain4-(N-fl-cyanoethyl-N-ethionylamino)-1-(4'-nitrobenzoylamino)-benzene.The latter is reduced to obtain 4-(N-fi-cyanoethyl-N-ethionylamino)-1-(4-aminobenzoylamino)-benzene in the form of a colorless powder.

The following table indicates the diazo and coupling components offurther azo dyestuffs which can be obtained in an analogous manner andthe tints obtained therewith on cotton.

Example 14 5.6 parts of 1-aminobenzene-2,S-disulfonic acid weredissolved in a mixture of 20 parts by volume of water, 18 parts byvolume of sodium carbonate solution of 10 weight-percent strength and 4parts by volume of a 5 N-solution of sodium nitrite and added to amixture of 50 parts by volume of 2 N-hydrochloric acid and 100 parts ofice. To the diazo solution so obtained 10 parts of the sodium salt of1-(2'-3'-hydroxynaphthoylamino)-3- (Ncarbmethoxymethyl-N-ethiouylamino)-benzene of v the following formula llom-o-o on were added and subsequently 16 parts of crystallized sodiumacetate and 3 parts of sodium carbonate were introduced. When thecoupling was complete the dyestuff was salted out with potassiumchloride and isolated.

The dyestuff constituted a red-orange powder which yielded orange printsof good fastness to washing on cotton.

Thel-(2-hydroxy-3-naphthoylamino)-3-(N-carb1nethoxymethyl-N-ethionylamino)-benzencused as the diazo component may be prepared by condensation of2-hydroxynaphthalene-3-carboxylic acid chloride with 3'-(N-carbmethoXymethyl-N-ethionylamino) -1-aminobenzene.

Example 15 To a mixture of 186 parts of cyanuric chloride, 150 parts byvolume of acetone and 200 parts by volume of water a neutral solution of31.9 parts of 1-hydroxy-8- 16 We claim: 1. A compound of the groupconsisting of compound of the formulae aminonaphthalene-3,6-disulfonicacid in 200 parts by volume of an aqueous potassium hydroxide solutionof about F 10 weight-percent strength was added at to C. Subsequently aneutral solution of 38.7 parts of the potassium salt of3-(N-,B-cyanoethyl-N-ethionylamino)-l-aminoben- R zone in 230 parts byvolume of water was run in at 10 (so H) to 50 C. By simultaneouslyadding 1 N-KOH the pH 3 m was maintained between 5 and 6 during bothcondensad tions.

17.3 parts of 2-aminobenzene sulfonic acid were dissolved in 100 partsby volume of water and 45 parts by F volume of 5 N-hydrochloric acid anddiazotized at a temn perature within the range of 0 to 5 C. by slowlyadding parts by volume of a 5 N solution of sodium nitrite. (301mm Whenthe diazotization was terminated, the pH was ad- 20 justed to 4.5 byadding potassium bicarbonate and the diazo solution was combined at 10C. with the condenh i F represents a monoazo or disazo dyestuifmolesation solution obtained as described above. The pH was culecontaining at least one benzene ring and a naphthol adjusted to 6.5 bythe addition of potassium bicarbonate. or pyrazolone group, the reactivegroup shown within the When the coupling was complete the dyestuffformed Was brackets being connected directly to a benzene ring, R saltedout with potassium chloride, filtered, Washed wi h represents a memberof the group consisting of a hydrogen saturated potassium chloridesolution and dried at 40 to atom and an alkyl group having 1 to 5 carbonatoms, X 50 C. in vacuo. represents a member of the group consisting ofan alkyl- The dyestufi" so obtained dissolved in water with a red enegroup having 1 to 4 carbon atoms and an alkylene color. It yieldedbright bluish red prints of very good group having 1 to 4 carbon atomssubstituted by a lower wet fastness properties on cotton. alkyl group, Yrepresents a member of the group consist- The following table indicatesthe condensation compoing of a cyano group, a carbomethoxy group, acarboxylic nents with cyanuric chloride and the diazo components of acidgroup and chlorine, Z represents a member of the further azo dyestuffsobtainable in analogous manner and group consisting of O--SO H, OOCCHand chlothe tints obtained therewith on cotton. rine, n stands for oneof the integers l and 2 and m stands 1st Condensation 2nd CondensationDiazo Component Tint on Cotton Component Component 1-hydr0xy-7-amino-34N-fl-cyanoethyl-N- 2-aminobenzene sul- Scarlet.

naphthalone-3- vinylsulfonylamjfonic acid. sulfonic acid.no)-1-aminobenl-hydroxy-G-amino- 3 l l g cyanoethyl-N-l-amino-naphthalene- Golden yellow.

naphthalene-3- ethionylarnino)-l- 2,5-disul1'onic acid. sull'onio acid.aminobenzene. l-hydroxy-B-aminodn Aniline Bluish red.

naphthalene-3,6- disulionio acid.

Example 16 for one of the integers l to 4.

22.3 parts of the dyestutf of the following formula SOaNa (obtainable bycoupling diazotized 4-(N-carbmethoxy-Inethyl-N-acetylamino)-1-aminobenzene withl-hydroxynaphthalene-4-sulfonic acid and subsequent saponificaition ofthe coupled product with dilute hydrochloric acid) were dissolved in 350parts by volume of water and cooled to a temperature of 0 to 5 C. Atthat temperature a mixture of 15 parts of fi-acetoxyethane sulfochlorideand 70 parts by volume of acetone was slowly run in, while stirringvigorously. By the simultaneous addition of sodium hydrogen carbonatethe pH was maintained within the range of 5.5 to 6.5. The mixture wasthen stirred at 20 C. until the conversion was complete. The acylateddyestulf was isolated. A red powder was obtained which yielded scarletprints of very good fastness to washing on cotton.

2. The compound of the formula 17 18 4. The compound of the formula 6.The compound of the formula OH =N /OHz-CHz-CN 5 CHK CO NH Ho s SO3H NSOzCHzOH2OS0 H 803E 5. The compound of the formula SOFCHQ'CHTO-S 03H OH-CO-NH OH 10 I No references cited.

N=N- @ij: CHARLES B. PARKER, Primary Examiner. H038 SOSH F. D. HIGEL,Assistant Examiner.

SOrCHz-CHr-O-SOaH 15

1. A COMPOUND OF THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULAE